EP1853528A1 - Reinforced structure comprising a cementitious matrix and zinc coated metal elements - Google Patents
Reinforced structure comprising a cementitious matrix and zinc coated metal elementsInfo
- Publication number
- EP1853528A1 EP1853528A1 EP05819220A EP05819220A EP1853528A1 EP 1853528 A1 EP1853528 A1 EP 1853528A1 EP 05819220 A EP05819220 A EP 05819220A EP 05819220 A EP05819220 A EP 05819220A EP 1853528 A1 EP1853528 A1 EP 1853528A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc coated
- coated metal
- cementitious matrix
- metal elements
- reinforced structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 122
- 239000011701 zinc Substances 0.000 title claims abstract description 76
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 76
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000011159 matrix material Substances 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000002787 reinforcement Effects 0.000 claims abstract description 12
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 7
- 150000003536 tetrazoles Chemical class 0.000 claims abstract description 7
- 150000003852 triazoles Chemical class 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims description 38
- 229910000831 Steel Inorganic materials 0.000 claims description 27
- 239000010959 steel Substances 0.000 claims description 27
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 4
- 238000004210 cathodic protection Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 description 22
- 239000004568 cement Substances 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 229920006334 epoxy coating Polymers 0.000 description 6
- 239000008397 galvanized steel Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011150 reinforced concrete Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 229910007570 Zn-Al Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011210 fiber-reinforced concrete Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000009417 prefabrication Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- CHADYUSNUWWKFP-UHFFFAOYSA-N 1H-imidazol-2-ylsilane Chemical compound [SiH3]c1ncc[nH]1 CHADYUSNUWWKFP-UHFFFAOYSA-N 0.000 description 1
- CDNHLXOFELOEOL-UHFFFAOYSA-N 3-methyl-1h-benzimidazole-2-thione Chemical compound C1=CC=C2N(C)C(S)=NC2=C1 CDNHLXOFELOEOL-UHFFFAOYSA-N 0.000 description 1
- 206010012434 Dermatitis allergic Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 201000008937 atopic dermatitis Diseases 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C3/00—Structural elongated elements designed for load-supporting
- E04C3/38—Arched girders or portal frames
- E04C3/44—Arched girders or portal frames of concrete or other stone-like material, e.g. with reinforcements or tensioning members
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/128—Heterocyclic nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/12—Multiple coating or impregnating
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
- E04C5/01—Reinforcing elements of metal, e.g. with non-structural coatings
- E04C5/012—Discrete reinforcing elements, e.g. fibres
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
- E04C5/01—Reinforcing elements of metal, e.g. with non-structural coatings
- E04C5/015—Anti-corrosion coatings or treating compositions, e.g. containing waterglass or based on another metal
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1075—Chromium-free or very low chromium-content materials
- C04B2111/1081—Chromium VI, e.g. for avoiding chromium eczema
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/26—Corrosion of reinforcement resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/249932—Fiber embedded in a layer derived from a water-settable material [e.g., cement, gypsum, etc.]
Definitions
- Reinforced structure comprising a cementitious matrix and zinc coated metal elements
- the invention relates to a cementitious matrix reinforced with zinc coated metal elements and to zinc coated metal elements for the reinforcement of a cementitious matrix.
- the invention further relates to a method to inhibit hydrogen gas evolution during the hardening of concrete reinforced with zinc coated metal elements.
- Galvanized steel fibers As bare steel fibers may suffer from corrosion, galvanized steel fibers have been proposed to give the fibers a long term corrosion resistance. Galvanized reinforcing steel elements are especially useful for the reinforcement of concrete for construction purposes whereby the reinforced concrete will be exposed to the weather before construction begins, as for example in prefabrication construction.
- the hydrogen gas evolution is leading to aesthetical problems as well as to strength and durability problems.
- the durability problem is the result of the reduction in the thickness of the zinc or zinc alloy coating due to the reaction of the zinc or zinc alloy coating in the alkaline environment.
- the problems of galvanized steel fibers in concrete are described in "Effect of chemical-physical interaction between galvanized steel fibres and concrete", T. Belleze, R. Fratesi, C. Failla, 6 th RILEM Symposium on Fibre-Reinforced Concretes (FRC) BEFIB 2004, 20-22 September 2004, 239-248.
- the zinc surfaces can be passivated. This can be realised by treating the galvanized steel elements with a chromium based compound. Also the chromate naturally present in the concrete can be sufficient to protect the galvanized steel elements.
- the epoxy coating acts solely as a barrier against a corrosive environment. If there are defects in the epoxy coating through which aggressive agents can penetrate the barrier, corrosion will concentrate on these areas. Defects in the coating will thus cause local hydrogen gas evolution and will result in a loss of bond strength. Integrity of the epoxy coating is therefore essential as the film must be free from pores, cracks and damaged areas. Epoxy coatings are fragile. Epoxy coated metal elements must therefore be handled with a lot of care during storing, transport and handling.
- a reinforced structure comprising a cementitious matrix and zinc coated metal elements is provided.
- the zinc coated metal elements are brought in the cementitious matrix and are surrounded by the cementitious matrix, creating an interface zinc coated metal element - cementitious matrix.
- the reinforced structure according to the present invention comprises at least at the interface of the zinc coated metal elements and the cementitious matrix a compound giving the zinc coated metal elements cathodic protection.
- the compound is selected from the group consisting of the imidazoles, the triazoles and the tetrazoles.
- the main function of this compound is to avoid the hydrogen gas evolution at the interface of the zinc coated metal elements and the cementitious matrix during the mixing, pouring, setting and/or hardening of the reinforced structure.
- the critical period in which the galvanized surface of the metal elements needs protection is the period in which the cementitious matrix is hardening, i.e. the first 24 hours till the first 72 hours after the casting.
- the compound according to the present invention is preferably present in a concentration between 0.005 and 2 %, for example between 0.04 and 0.2 %.
- the concentration is expressed in wt % relative to the mixing water used to prepare the cementitious matrix.
- the imidazole comprises silyl-imidazole such as N-(trimethylsilyl)-imidazole or benzimidazole, such as 2-mercaptobenzimidazole or 2-mercapto-1- methylbenzimidazole.
- the compound has to be present at least at the interface of the zinc coated metal elements and the cementitious matrix.
- the compound is applied on the zinc coated metal elements before these metal elements are introduced in the cementitious matrix.
- the compound can for example be incorporated in a coating layer applied on the zinc coated metal element before these elements are introduced in the cementitious matrix.
- the compound can be added to a glue applied on the zinc coated metal elements before these metal elements are introduced in the cementitious matrix.
- the compound is added to the cementitious matrix or to at least one component of the cementitious matrix and the zinc coated metal elements are introduced to the cementitious matrix comprising this compound.
- a great advantage of a reinforced structure according to the present invention is that the reinforced structure is free of hexavalent chromium as hexavalent chromium is not required to protect the zinc coated metal elements. This means that the metal elements do not require a treatment with a chromium based compound.
- a further advantage of a reinforced structure according to the present invention is that a good protection of the zinc coated metal elements is also obtained in case cement free of hexavalent chromium is used. Up to now, even in case no chromium base compounds are added to protect the zinc coated metal elements, zinc coated metal elements could take advantage of the chromium naturally present in cement.
- New legislation is imposing to limit the amount of hexavalent chromium in cement to minimize the occurrence of chromate related allergic dermatitis. Consequently, zinc coated metal elements in a cementitious matrix can no longer take advantage of the chromium naturally present in cement.
- cementitious matrix should be understood to mean the matrix material apart from the metal elements.
- the cementitious matrix may comprise any material comprising cement as for example concrete or mortar.
- Metal elements should be understood to mean the elements reinforcing the cementitious matrix.
- the metal element may comprise any kind of metal reinforcement element such as a metal wire, metal cord, metal fiber, a metal bar, metal sheet or metal mesh.
- the metal element may be made of any metal or metal alloy known in the art.
- the metal elements are preferably made of steel.
- Preferred metal elements to reinforce a cementitious matrix are steel fibers sold amongst others by the applicant NV Bekaert SA under the brand name DRAMIX.
- steel fibers are used with a tensile strength comprised e.g. between 500 and 3000 N/mm 2 .
- the used fibers can e.g. be straight.
- the fibers have a form that makes it rather difficult to pull them out of the hardened cementitious matrix using a tensile strain.
- the fibers are e.g. hooked end, corrugated or their cross-section-surface varies along the length.
- the thickness or diameter preferably varies from 0.1 to 1.2 mm.
- the length-diameter ratio for steel fibers is, for practical and economical reasons, mostly situated between 10 and 200 and preferably minimally amounts to 40.
- the length is the rectilinear distance between the ends of the fibers, whereas the diameter of fibers of which the diameter varies along the length is defined as the average diameter over the entire length.
- the zinc coated metal elements may have a zinc or zinc alloy coating.
- zinc alloy coating one can consider for example Zn-Fe, Zn-Ni, Zn-Al, Zn-Mg, Zn-Mg-Al alloys.
- a preferred zinc alloy coating is a Zn-Al alloy coating comprising between 2 and 15 % Al. Possibly, between 0.1 and 0.4 % of a rare earth element such as Ce and/or La can be added.
- the reinforced structure according to the present invention can be used for any application known in the art such as prefabrication constructions, bridges, buildings, tunnels, parking garages, offshore oil platform, ...
- a zinc coated metal element for the reinforcement of a cementitious matrix is provided.
- the zinc coated metal element is coated with a layer comprising a compound selected from the group consisting of the imidazoles, the triazoles and the tetrazoles.
- the coating layer comprises for example a glue comprising said compound.
- the metal element may comprise any kind of metal reinforcement element such as a metal wire, metal cord, metal fiber, metal bar, metal sheet or metal mesh.
- the metal element may be made of any metal or metal alloy known in the art.
- the metal elements are preferably made of steel.
- Preferred metal elements are steel fibers.
- a method to inhibit hydrogen gas evolution at the interface of zinc coated metal elements embedded in a cementitious matrix comprises the steps of providing zinc coated metal elements, introducing said zinc coated metal elements in a cementitious matrix, and treating said zinc coated metal elements and/or said cementitious matrix with a compound selected from the group consisting of the imidazoles, the triazoles and the tetrazoles.
- the method according to the present invention is avoiding hydrogen gas evolution during the mixing, pouring, setting and/or hardening of the reinforced structure.
- the critical period in which the galvanized surface of the metal elements needs protection is the period in which the cementitious matrix is hardening, i.e. the first 24 hours till the first 72 hours after the casting.
- the treatment with said compound may comprise any technique that allows bringing the zinc coated metal elements and the cementitious matrix at least at their interface in contact with the above-mentioned compound.
- the compound can for example be added to the cementitious matrix.
- the compound can be added by applying a coating layer comprising this compound on the zinc coated metal elements before this zinc coated metal elements are introduced in the cementitious matrix.
- the compound is added to a glue applied on a zinc coated metal element or on a number of zinc coated metal elements before the zinc coated metal elements are introduced in the cementitious matrix.
- the glue is chosen in such a way that it is dissolving, melting, softening or breaking mechanically once it is added to the cementitious matrix, so that the strips come to disintegrate into separate fibers and are equally distributed over the cementitious matrix.
- FIG. 1 is an illustration of the measurement of the potential in a fresh construction matrix
- FIG. 1 shows the open circuit potential (OCP) of three different samples in function of time.
- the wet concrete is acting as the electrolyte in which corrosion may occur.
- Water is capable of decomposing into hydrogen and oxygen.
- the decomposition of water is an electrochemical redox reaction which occurs at a certain potential.
- the electrochemical potential at which the decomposition takes place is determined by the pH according to the law of Nernst.
- the element When a strong electronegative element like zinc, aluminium or magnesium is exposed to water, the element has an open circuit potential as defined in the standard ASTM G 15-93.
- the open circuit potential is also referred to as rest potential or standard potential.
- the open circuit potential drops below the hydrogen evolution potential and hence initiates the reduction of hydrogen ions resulting in hydrogen gas evolution.
- the hydrogen evolution is calculated, based on a pH measurement of the environment whereto the material will be exposed.
- the pH is of a cementitious matrix is measured according to test method
- ASTM G51-95 This method covers a procedure for determining the pH of a soil in corrosion testing.
- ASTM G51-95 is applied for a cementitious matrix instead of a soil.
- a pH of 13.04 was found for a sample comprising one part cement and four parts sand (instead of soil according to ASTM51-95).
- the open circuit potential can be measured in situ according to standard ASTM C876. However it is more appropriate to measure the open circuit potential in a small sample as for example shown in Figure 1.
- the equipment is used according to standard ASTM G3-89(94).
- a zinc coated metal element 12 is embedded in a cementitious matrix 14.
- the electrical potential between the zinc coated metal element 12 and a reference electrode 16 is measured by means of an electrometer or high impedance voltmeter 18.
- the three samples all comprise a cementitious matrix obtained by mixing one part of CEM Il 42.5R cement with four parts of sand and 5 parts of water.
- sample 2 comprises chromium treated steel fibers
- - sample 3 comprises steel fibers treated with benzimidazole.
- the pH of the cementitious matrix was determined. A pH value of 12.25 was found. According to the law of Nernst, the EH 2 is determined to be :
- the open circuit potential of the three samples in function of the time was measured and is given in Figure 2.
- the open circuit potential of sample 1 is given by line 21
- the open circuit potential of sample 2 is given by line 22
- the open circuit potential of sample 3 is given by line 23.
- Beams (150 x 150 x 500 mm) reinforced with steel fibers are subjected to the test.
- the concrete composition is the same for the sample 1 and 2.
- the dosage of the steel fibers is 20 and 40 kg/m 3 .
- the steel fibers added to the concrete in sample 1 to 2 are treated in a different way :
- - sample 1 comprises zinc coated steel fibers treated with a corrosion inhibitor according to the present invention
- - sample 2 comprises zinc coated steel fibers without further treatment.
- the beams are stored in moist atmosphere during 28 days.
- the results of the load test are given in Table 1 for a dosage of 20 kg/m 3 and in Table 2 for a dosage of 40 kg/m 3 .
- Zinc coated steel fibers treated according to the present invention give an increase in toughness of about 10-40 % , for example 30 %, compared to non treated zinc coated steel fibers.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Architecture (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
- Reinforcement Elements For Buildings (AREA)
- Catalysts (AREA)
- Laminated Bodies (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Chemically Coating (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SI200532258T SI1853528T1 (en) | 2004-12-23 | 2005-12-16 | Reinforced structure comprising a cementitious matrix and zinc coated metal elements |
PL05819220T PL1853528T3 (en) | 2004-12-23 | 2005-12-16 | Reinforced structure comprising a cementitious matrix and zinc coated metal elements |
EP05819220.4A EP1853528B1 (en) | 2004-12-23 | 2005-12-16 | Reinforced structure comprising a cementitious matrix and zinc coated metal elements |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04106930 | 2004-12-23 | ||
PCT/EP2005/056868 WO2006067095A1 (en) | 2004-12-23 | 2005-12-16 | Reinforced structure comprising a cementitious matrix and zinc coated metal elements |
EP05819220.4A EP1853528B1 (en) | 2004-12-23 | 2005-12-16 | Reinforced structure comprising a cementitious matrix and zinc coated metal elements |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1853528A1 true EP1853528A1 (en) | 2007-11-14 |
EP1853528B1 EP1853528B1 (en) | 2019-06-26 |
Family
ID=34930143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05819220.4A Active EP1853528B1 (en) | 2004-12-23 | 2005-12-16 | Reinforced structure comprising a cementitious matrix and zinc coated metal elements |
Country Status (17)
Country | Link |
---|---|
US (2) | US7871695B2 (en) |
EP (1) | EP1853528B1 (en) |
JP (1) | JP5090927B2 (en) |
KR (1) | KR101186923B1 (en) |
CN (1) | CN101087738B (en) |
AU (1) | AU2005318230B2 (en) |
BR (1) | BRPI0519435B1 (en) |
DK (1) | DK1853528T3 (en) |
ES (1) | ES2738485T3 (en) |
HU (1) | HUE045616T2 (en) |
MX (1) | MX2007007643A (en) |
PL (1) | PL1853528T3 (en) |
PT (1) | PT1853528T (en) |
RU (1) | RU2007127912A (en) |
SI (1) | SI1853528T1 (en) |
TR (1) | TR201911285T4 (en) |
WO (1) | WO2006067095A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022136646A1 (en) | 2020-12-23 | 2022-06-30 | Nv Bekaert Sa | Post-tensioned concrete with fibers for long strips |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX2007007643A (en) * | 2004-12-23 | 2007-08-06 | Bekaert Sa Nv | Reinforced structure comprising a cementitious matrix and zinc coated metal elements. |
EP2367990A1 (en) * | 2008-12-18 | 2011-09-28 | NV Bekaert SA | A cord for reinforcement of a cementitious matrix |
US20140136210A1 (en) * | 2012-11-14 | 2014-05-15 | At&T Intellectual Property I, L.P. | System and method for robust personalization of speech recognition |
BE1023245B1 (en) * | 2015-12-04 | 2017-01-10 | Anatis Sa | Tank and bio-methanation plant |
KR20210152512A (en) | 2019-04-12 | 2021-12-15 | 엔브이 베카에르트 에스에이 | Coated Steel Fibers for Cement Matrix Reinforcement |
WO2024035676A1 (en) | 2022-08-11 | 2024-02-15 | Pensmore Reinforcement Technologies, Llc | Protected metal wires and fibers for reinforcement of concrete structures |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3619441A (en) * | 1969-04-03 | 1971-11-09 | Southern Block And Pipe Corp | Metal treatment to prevent corrosion and blemishes in metal reinforced concrete structures |
JPS52141013A (en) * | 1976-05-20 | 1977-11-25 | Sumitomo Metal Ind | Zinc placed steel fiber for strengthening concrete |
JPS5378625A (en) * | 1976-12-21 | 1978-07-12 | Sumitomo Metal Ind | Steel fibers for reinforcing concrete |
JPS5472223A (en) * | 1977-11-22 | 1979-06-09 | Tokuyama Soda Kk | Antirust agent for mortar or concrete |
DE3133882A1 (en) * | 1981-07-20 | 1983-02-03 | Sika AG, vorm. Kaspar Winkler & Co., 8048 Zürich | PROCESS FOR CORROSION PROTECTION OF ARMORING IRON, TENSION CABLES AND THE LIKE IN COMPONENTS |
JPS61141650A (en) * | 1984-12-12 | 1986-06-28 | 株式会社神戸製鋼所 | Anticorrosion for zinc-plated steel member |
JPS6263686A (en) * | 1985-09-12 | 1987-03-20 | Kanzaki Paper Mfg Co Ltd | Volatile corrosion inhibitor |
JP2571620B2 (en) * | 1989-03-17 | 1997-01-16 | 日立電線株式会社 | Manufacturing method of corrosion resistant zinc alloy coated steel wire |
DE4002471C2 (en) * | 1990-01-29 | 1993-10-21 | Riedel De Haen Ag | Use of a microbiocidal agent in the manufacture of concrete roof tiles |
JP3362201B2 (en) * | 1991-09-06 | 2003-01-07 | 大塚化学株式会社 | Rust prevention composition for zinc sheet or zinc-based surface-treated steel sheet |
DE69400509T2 (en) * | 1993-06-23 | 1997-04-10 | Sumitomo Metal Ind | Metal sheet with a galvanically produced zinc or zinc alloy dispersion coating and method for producing the same |
US5346962A (en) * | 1993-11-03 | 1994-09-13 | Bridgestone/Firestone, Inc. | Elastomers having reduced hysteresis prepared with vinyl imidazole |
US5597514A (en) | 1995-01-24 | 1997-01-28 | Cortec Corporation | Corrosion inhibitor for reducing corrosion in metallic concrete reinforcements |
FR2736935B1 (en) * | 1995-07-21 | 1997-08-14 | Lorraine Laminage | AQUEOUS TREATMENT AGAINST CORROSION OF STEEL SHEETS COATED ON A ZINC OR ZINC ALLOY SIDE |
US5744239A (en) * | 1996-09-27 | 1998-04-28 | Minnesota Mining And Manufacturing Company | Addition of antimicrobial agents to pavement marking materials |
FR2771088B1 (en) * | 1997-11-17 | 2000-01-21 | Jean Dominique Ceccaldi | NON-WITHDRAWAL CONCRETE OR MORTAR |
US6075072A (en) * | 1998-03-13 | 2000-06-13 | 3M Innovative Properties Company | Latent coating for metal surface repair |
FR2778186B1 (en) * | 1998-05-04 | 2000-06-23 | Elf Antar France | WATER-SOLUBLE COMPOSITION AS A COATING OF METAL SURFACES IN THE FORM OF DRY FILMS TIGHT TO ATMOSPHERIC CORROSION |
US6627117B2 (en) * | 1998-06-09 | 2003-09-30 | Geotech Chemical Company, Llc | Method for applying a coating that acts as an electrolytic barrier and a cathodic corrosion prevention system |
US6197805B1 (en) * | 1999-05-27 | 2001-03-06 | Troy Technology Corporation, Inc. | Broad spectrum antimicrobial mixtures |
JP4183999B2 (en) * | 2002-07-29 | 2008-11-19 | 日鉱金属株式会社 | Surface treatment agent containing imidazole alcohol as an active ingredient |
US6897191B2 (en) * | 2003-04-30 | 2005-05-24 | Specialty Construction Brands, Inc. | Disinfecting, antimicrobial sealing compositions and methods of using the same |
EP1504891A1 (en) * | 2003-08-06 | 2005-02-09 | Elisha Holding LLC | Multilayer coated corrosion resistant article and method of production thereof |
MX2007007643A (en) * | 2004-12-23 | 2007-08-06 | Bekaert Sa Nv | Reinforced structure comprising a cementitious matrix and zinc coated metal elements. |
-
2005
- 2005-12-16 MX MX2007007643A patent/MX2007007643A/en active IP Right Grant
- 2005-12-16 AU AU2005318230A patent/AU2005318230B2/en active Active
- 2005-12-16 KR KR1020077013711A patent/KR101186923B1/en active IP Right Grant
- 2005-12-16 RU RU2007127912/03A patent/RU2007127912A/en unknown
- 2005-12-16 PT PT05819220T patent/PT1853528T/en unknown
- 2005-12-16 TR TR2019/11285T patent/TR201911285T4/en unknown
- 2005-12-16 CN CN2005800444938A patent/CN101087738B/en active Active
- 2005-12-16 WO PCT/EP2005/056868 patent/WO2006067095A1/en active Application Filing
- 2005-12-16 SI SI200532258T patent/SI1853528T1/en unknown
- 2005-12-16 PL PL05819220T patent/PL1853528T3/en unknown
- 2005-12-16 BR BRPI0519435A patent/BRPI0519435B1/en not_active IP Right Cessation
- 2005-12-16 JP JP2007547471A patent/JP5090927B2/en active Active
- 2005-12-16 HU HUE05819220A patent/HUE045616T2/en unknown
- 2005-12-16 EP EP05819220.4A patent/EP1853528B1/en active Active
- 2005-12-16 DK DK05819220.4T patent/DK1853528T3/en active
- 2005-12-16 ES ES05819220T patent/ES2738485T3/en active Active
- 2005-12-16 US US11/722,434 patent/US7871695B2/en active Active
-
2010
- 2010-12-21 US US12/974,389 patent/US20110088596A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO2006067095A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022136646A1 (en) | 2020-12-23 | 2022-06-30 | Nv Bekaert Sa | Post-tensioned concrete with fibers for long strips |
Also Published As
Publication number | Publication date |
---|---|
SI1853528T1 (en) | 2019-08-30 |
DK1853528T3 (en) | 2019-09-23 |
BRPI0519435A2 (en) | 2009-01-20 |
US20100021759A1 (en) | 2010-01-28 |
CN101087738B (en) | 2010-11-10 |
AU2005318230B2 (en) | 2010-12-16 |
MX2007007643A (en) | 2007-08-06 |
HUE045616T2 (en) | 2020-01-28 |
RU2007127912A (en) | 2009-01-27 |
AU2005318230A1 (en) | 2006-06-29 |
PL1853528T3 (en) | 2020-08-10 |
EP1853528B1 (en) | 2019-06-26 |
KR101186923B1 (en) | 2012-09-28 |
PT1853528T (en) | 2019-08-06 |
JP2008525293A (en) | 2008-07-17 |
BRPI0519435B1 (en) | 2016-06-07 |
US7871695B2 (en) | 2011-01-18 |
JP5090927B2 (en) | 2012-12-05 |
CN101087738A (en) | 2007-12-12 |
ES2738485T3 (en) | 2020-01-23 |
US20110088596A1 (en) | 2011-04-21 |
KR20070093982A (en) | 2007-09-19 |
TR201911285T4 (en) | 2019-08-21 |
WO2006067095A1 (en) | 2006-06-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Bentur et al. | Steel corrosion in concrete: fundamentals and civil engineering practice | |
US20110088596A1 (en) | Reinforced structure comprising a cementitious matrix and zinc coated metal elements | |
Nürnberger | Corrosion induced failure mechanisms of prestressing steel | |
Khomwan et al. | Startup Thailand: A new innovative sacrificial anode for reinforced concrete structures | |
Topcu et al. | Experimental investigation of utilizing chemical additives and new generation corrosion inhibitors on reinforced concrete | |
Yeomans | Comparative studies of galvanized and epoxy coated steel reinforcement in concrete | |
Evaluation of Multiple Corrrosion Protection Systems and Corrosion Inhibitors for Reinforced Concrete Bridge Decks | ||
Ravindrarajah et al. | Corrosion of steel in concrete in relation to bar diameter and cover thickness | |
Hartt | Protocol for Projecting Time-to-Corrosion of Reinforcing Steel in Concrete Exposed to Chlorides | |
US8336285B2 (en) | Cord for reinforcement of a cementitious matrix | |
Sistonen | Service life of hot-dip galvanised reinforcement bars in carbonated and chloride-contaminated concrete | |
Kayali | Bond of steel in concrete and the effect of galvanizing | |
Hamad et al. | Effect of confinement on bond strength of hot-dip galvanized lap splices in high-strength concrete | |
Yeomans | Laboratory and field performance of galvanized steel in concrete | |
Van Tittelboom et al. | Self-healing of concrete cracks by the release of embedded water repellent agents and corrosion inhibitors to reduce the risk for reinforcement corrosion | |
Aydin et al. | Effect of hot dip galvanized coating on the corrosion resistance of the external surface of reinforcement steel | |
O’Reilly | Performance of multiple corrosion protection systems for reinforced concrete bridge decks | |
VON HOCHLEISTUNGSBETON | Structural behaviour of high performance concrete | |
Ma | Effects of Mild Corrosion on the Tensile Strength of Reinforced Concrete Specimens with Transverse Cracks | |
Ezeokpube et al. | APPLICATION OF WENNER TECHNIQUE IN ASSESSMENT OF STEEL BAR MECHANICAL PROPERTIES IN CHLORIDE-INDUCED CORROSION OF CONCRETE STRUCTURES | |
Yeomans | Coated steel reinforcement in concrete | |
Pazini et al. | Protection Corrosion Mechanisms Involved in Repair Systems with Surface Coatings on Reinforced Cement | |
Saqan et al. | Enhancing the Life Cycle of RC Structures and Validating Service Life Prediction Models | |
Batis et al. | Investigation of the protective effect of repair mortars with migrating corrosion inhibitor in deterioration of structural damage | |
Ganz | Effect of zinc on prestressing steel: Technical report |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20070525 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
17Q | First examination report despatched |
Effective date: 20071119 |
|
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20190215 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1148092 Country of ref document: AT Kind code of ref document: T Effective date: 20190715 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602005055974 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Ref document number: 1853528 Country of ref document: PT Date of ref document: 20190806 Kind code of ref document: T Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20190730 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 Effective date: 20190919 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190626 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190626 |
|
REG | Reference to a national code |
Ref country code: SK Ref legal event code: T3 Ref document number: E 31888 Country of ref document: SK |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190927 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190926 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190626 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2738485 Country of ref document: ES Kind code of ref document: T3 Effective date: 20200123 |
|
REG | Reference to a national code |
Ref country code: HU Ref legal event code: AG4A Ref document number: E045616 Country of ref document: HU |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190626 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190626 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20191026 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200224 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602005055974 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: UEP Ref document number: 1148092 Country of ref document: AT Kind code of ref document: T Effective date: 20190626 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG2D | Information on lapse in contracting state deleted |
Ref country code: IS |
|
26N | No opposition filed |
Effective date: 20200603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190626 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190626 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20221215 Year of fee payment: 18 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230619 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SK Payment date: 20231211 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20231220 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SI Payment date: 20231207 Year of fee payment: 19 Ref country code: SE Payment date: 20231220 Year of fee payment: 19 Ref country code: PT Payment date: 20231207 Year of fee payment: 19 Ref country code: NL Payment date: 20231220 Year of fee payment: 19 Ref country code: LU Payment date: 20231220 Year of fee payment: 19 Ref country code: IT Payment date: 20231228 Year of fee payment: 19 Ref country code: IE Payment date: 20231220 Year of fee payment: 19 Ref country code: HU Payment date: 20231222 Year of fee payment: 19 Ref country code: FR Payment date: 20231221 Year of fee payment: 19 Ref country code: DK Payment date: 20231227 Year of fee payment: 19 Ref country code: DE Payment date: 20231214 Year of fee payment: 19 Ref country code: CZ Payment date: 20231211 Year of fee payment: 19 Ref country code: AT Payment date: 20231221 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20231212 Year of fee payment: 19 Ref country code: BE Payment date: 20231220 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20240124 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20240102 Year of fee payment: 19 |